Fanidan bajargan mavzu: uglevodlar rahbar: M. Hojimatov
Download 0.7 Mb. Pdf ko'rish
|
nitrobirikmalar
- Bu sahifa navigatsiya:
- I.3. Murakkab uglevodlar yoki polisaxaridlar. Poliozalar
|
I.2.3. Fizik xossalari. Monosaxaridlar kristall moddalar bo’lib, ko’pchiligi gigroskopik, suvda yaxshi eriydi. Ularning eritmalari lakmusga neytral bo’ladi, ular shirin ta’mga ega. Optik jihatdan faol. Monosaxaridllar spirtda yomon, efirda esa mutlaqo erimaydi. I.2.4. Kimyoviy xossalari. Ma’lumki, har bir monosaxarid eritmada har xil tautomer shakllarda bo’ladi. Shuning uchun ham kimyoviy reaksiyalarda reaksiya sharoitiga hamda ta’sir qilayotgan reagentning tabiatiga qarab monosaxaridlarning formulasi u yoki bu shaklda ifodalanadi. Ya’ni, monosaxaridlar spirtlarni, karbonilli birikmalarni va yarimatsetallarni xossalarini takrorlaydi. 1. Monosaxaridlarning qaytarilishi. Monosaxaridlar vodorod, litiy, aluminiy gidrid, natriy, bor gidrid ta’sirida qaytarilganda ko’p atomli spirtga aylanadilar.
CHO OH OH OH H H H H HO CH 2 OH [H] CH 2 OH OH OH OH H H H H HO CH 2 OH CHO OH OH OH H H H H HO CH 2 OH [H] CH 2 OH OH OH OH H H H H HO CH 2 OH
2. Monosaxaridlarning oksidlanishi. Monosaxaridlar oksidlanganda bir yoki ikki asosli oksikislotalarni hosil qiladilar.
HOH + Br 2 HBr + HOBr C 6
12 O 6 + HOBr CH 2 OH – (CHOH) 4 – COOH
HOH + Br 2 HBr + HOBr HOH + Br 2 HBr + HOBr C 6 H 12 O 6 + HOBr CH 2 OH – (CHOH) 4 – COOH
C 6 H 12 O 6 + HOBr CH 2 OH – (CHOH) 4 – COOH
11
Oksidlovchi sifatida gipoxlorid yoki gipobromid kislotalardan foydalaniladi: Ajralib chiqadigan HBr kalsiy yoki bariy karbonat bilan neytrallanadi.
3. Oksinitril sintezi. Bu reaksiya yordamida quyi monosaxaridlardan yuqori monosaxaridlar hosil qilish mumkin. Buni glukozadan D-geptoza hosil qilish misolida ko’rib chiqamiz:
CHO OH OH OH H H H H HO CH 2 OH HCN OH OH OH H H H H HO CH 2 OH OH H CN 2H 2 O -NH 3 OH OH OH H H H H HO CH 2 OH OH H COOH -H 2 O OH OH H H H H HO CH 2 OH OH H O = C
OH OH OH H H H H HO CH 2 OH OH H CN OH OH OH H H H H HO CH 2 OH OH H CHO H 2 -лактон
Д-гептоза CHO
OH OH OH H H H H HO CH 2 OH HCN OH OH OH H H H H HO CH 2 OH OH H CN OH OH OH H H H H HO CH 2 OH OH H CN 2H 2 O -NH
3 OH OH OH H H H H HO CH 2 OH OH H COOH OH OH OH H H H H HO CH 2 OH OH H COOH
-H 2 O OH OH H H H H HO CH 2 OH OH H O = C OH OH OH H H H H HO CH 2 OH OH H CN OH OH OH H H H H HO CH 2 OH OH H CN OH OH OH H H H H HO CH 2 OH OH H CHO OH OH OH H H H H HO CH 2 OH OH H CHO H 2 -лактон Д-гептоза
4.
Gidroksilaminning ta’siri. Bu reaksiya yordamida yuqori monosaxaridlardan quyi monosaxaridlarga o’tish mumkin bo’ladi:
CHO OH OH OH H H H H HO CH 2 OH H 2 NOH
-H 2 O CH = N – OH OH OH OH H H H H HO CH 2 OH -H 2 O C N OH OH OH H H H H HO CH 2 OH -H 2 O AgOH -AgCN CHO
OH OH H H H HO CH 2 OH Д-глюкоза Оксим
Оксинитрил Арабиноза CHO OH
OH H H H H HO CH 2 OH H 2 NOH -H 2 O CH = N – OH OH OH OH H H H H HO CH 2 OH -H 2 O C N OH OH OH H H H H HO CH 2 OH -H 2 O AgOH -AgCN CHO
OH OH H H H HO CH 2 OH CHO OH OH OH H H H H HO CH 2 OH H 2 NOH -H 2 O CH = N – OH OH OH OH H H H H HO CH 2 OH -H 2 O C N OH OH OH H H H H HO CH 2 OH -H 2 O AgOH -AgCN CHO
OH OH H H H HO CH 2 OH CHO OH OH H H H HO CH 2 OH Д-глюкоза Оксим Оксинитрил Арабиноза
12
5. Fenilgidrazin ta’siri. Bu reaksiya yordamida aldozalardan ketozalarni hosil qilish mumkin: CHO
OH OH OH H H H H HO CH 2 OH H 2 N-NHC
6 H 5 -H 2 O CH = N – NHC 6 H 5 OH OH OH H H H H HO CH 2 OH 2H 2 N-NHC 6 H 5 (-C 6 H 5 NH 2 ; NH 3 ; H 2 O) -H 2 O CH=N – NHC 6 H 5 OH OH H H H H HO CH 2 OH -2H
2 N – NHC
6 H 5 2H 2 O C=N – NHC 6 H 5 CHO
OH OH H H H HO CH 2 OH C = O [H]
CH 2 OH OH OH H H H HO CH 2 OH C = O манноза
фенилгидразон озазон
кетальдегид Д-фруктоза CHO OH
OH H H H H HO CH 2 OH H 2 N-NHC 6 H 5 -H 2 O CH = N – NHC 6 H 5 OH OH OH H H H H HO CH 2 OH 2H 2 N-NHC 6 H 5 (-C 6 H 5 NH 2 ; NH 3 ; H 2 O) -H 2 O CH=N – NHC 6 H 5 OH OH H H H H HO CH 2 OH -2H
2 N – NHC
6 H 5 2H 2 O C=N – NHC 6 H 5 CHO
OH OH H H H HO CH 2 OH C = O [H]
CH 2 OH OH OH H H H HO CH 2 OH C = O манноза
фенилгидразон озазон
кетальдегид Д-фруктоза
izomerlanadilar. Masalan, glukoza ishqor ta’sirida fruktoza va mannozga izomerlanadi:
CHO
OH OH OH H H H H HO CH 2 OH OH – CH – OH OH OH
H H HO CH 2 OH C = O CH 2 OH OH OH H H H HO CH 2 OH C = O
CHO H OH OH H H H HO HO CH 2 OH Д-фруктоза манноза
CHO OH OH OH H H H H HO CH 2 OH OH – CH – OH OH OH H H H HO CH 2 OH C = O CH 2 OH OH OH H H H HO CH 2 OH C = O
CHO H OH OH H H H HO HO CH 2 OH CHO H OH OH H H H HO HO CH 2 OH Д-фруктоза манноза
7. Alkillash reaksiyasi. Monosaxaridlar alkillanganda ular yarimatsetallar shaklida reaksiyaga kirishadilar, ularga metil spirti bilan xlorid kislota aralashmasi ta’sir ettirilganda alkillash glukozid gidroksili hisobiga boradi. Metil xlorid bilan kumush oksidi aralashmasi ta’sir ettirilganda esa
13
O CH 2 OH H H H H H OH OH OH HO СH 3 OH HCl O CH 2 OH H H H H H OH OH OCH 3 HO СH 3 Cl Ag 2 O O CH 2 OCH 3 H H H H H OCH
3 OCH
3 OCH
3 H 3 CO кислотали гидролизлаш - H
2 O, H
+ O CH 2 OCH
3 H H H H H OCH 3 OCH 3 OH H 3 CO O CH 2 OH H H H H H OH OH OH HO O CH 2 OH H H H H H OH OH OH HO СH 3 OH HCl
O CH 2 OH H H H H H OH OH OCH 3 HO O CH 2 OH H H H H H OH OH OCH
3 HO СH 3 Cl Ag 2 O O CH 2 OCH 3 H H H H H OCH 3 OCH 3 OCH
3 H 3 CO кислотали гидролизлаш - H
2 O, H
+ O CH 2 OCH
3 H H H H H OCH 3 OCH 3 OH H 3 CO O CH 2 OCH 3 H H H H H OCH 3 OCH 3 OCH
3 H 3 CO кислотали гидролизлаш - H
2 O, H
+ O CH 2 OCH
3 H H H H H OCH 3 OCH 3 OH H 3 CO O CH 2 OH H H H H H OH OH OH HO +5(CH 3 CO) 2 O -5CH 3 COOH
O CH 2 OCOCH 3 H H H H H OCOCH
3 OCOCH
3 OCOCH
3 H 3 COCO O CH 2 OH H H H H H OH OH OH HO O CH 2 OH H H H H H OH OH OH HO +5(CH 3 CO) 2 O -5CH 3 COOH
O CH 2 OCOCH 3 H H H H H OCOCH
3 OCOCH
3 OCOCH
3 H 3 COCO O CH 2 OCOCH
3 H H H H H OCOCH 3 OCOCH 3 OCOCH
3 H 3 COCO qolgan 4 ta gidroksil guruhi alkillanadi va pentametil-D-glyukozani hosil qiladi.
8. Glukozaga sirka angidridi bilan ta’sir ettirilganda pentaatsetilglukoza hosil bo’ladi:
9. Degidratlash reaksiyasi. Pentozalarga suyultirilgan sulfat kislota qo’shib qizdirilganda furfurol, geksozalardan oksimetilfurfurol hosil bo’ladi. Oksimetilfurfurol beqaror bo’lganligi sababli gidrolizlanib lavulin kislotaga aylanadi:
14
HO – CH – CH – OH H – CH C –
H CHO
OH HO O CHO фурфурол
H + -3H 2 O HO – CH – CH – OH HO – CH 2 CH CHO OH HOCH 2 -3H
2 O O CHO HOH
2 C -оксиметилфурфурол CH – CH
HO – C CH
CHO OH HOCH 2 CH 2 – CH 2 CO CO CHO
HOCH 2 CH 2 – CH
2 CO
COOH CH 3 + HCOOH Левулин кислота HO – CH – CH – OH H – CH
C – H
CHO OH HO O CHO
фурфурол H + -3H 2 O HO – CH – CH – OH HO – CH
2 CH
CHO OH HOCH 2 -3H
2 O O CHO HOH
2 C -оксиметилфурфурол HO – CH – CH – OH H – CH C –
H CHO
OH HO O CHO фурфурол
HO – CH – CH – OH H – CH
C – H
CHO OH HO O CHO
HO – CH – CH – OH H – CH
C – H
CHO OH HO HO – CH – CH – OH H – CH
C – H
CHO OH HO O CHO
O CHO
фурфурол H + -3H 2 O HO – CH – CH – OH HO – CH
2 CH
CHO OH HOCH 2 -3H
2 O O CHO HOH
2 C -оксиметилфурфурол HO – CH – CH – OH HO – CH 2
CHO OH HOCH 2 -3H
2 O O CHO HOH
2 C HO – CH – CH – OH HO – CH 2 CH CHO OH HOCH 2 -3H
2 O O CHO HOH
2 C O CHO HOH
2 C -оксиметилфурфурол CH – CH
HO – C CH
CHO OH HOCH 2 CH 2 – CH 2 CO CO CHO
HOCH 2 CH 2 – CH
2 CO
COOH CH 3 + HCOOH Левулин кислота CH – CH HO – C
CH CHO
OH HOCH
2 CH 2 – CH 2 CO CO CHO
HOCH 2 CH 2 – CH
2 CO
COOH CH 3 + HCOOH CH – CH
HO – C CH
CHO OH HOCH 2 CH 2 – CH 2 CO CO CHO
HOCH 2 CH – CH HO – C CH
CHO OH HOCH 2 CH 2 – CH 2 CO CO CHO
HOCH 2 CH 2 – CH
2 CO
COOH CH 3 + HCOOH CH 2 – CH 2 CO COOH CH 3 + HCOOH Левулин кислота
10. Monosaxaridlarning bijg’ishi. Monosaxaridlar fermentlar ishtirokida bijg’iganda oxirigi mahsulot sifatida ishlatilayotgan fermentning turiga qarab etil spirti, atseton, glitserin va boshqa mahsulotlar hosil bo’lishi mumkin:
Monosaxaridlar oziq-ovqat sanoatida ahamiyatga ega. I.3. Murakkab uglevodlar yoki polisaxaridlar. Poliozalar Download 0.7 Mb. Do'stlaringiz bilan baham: 
|